CN110088072B - Novel compound, semiconductor material, film using same, and semiconductor manufacturing method - Google Patents

Abstract

The present invention provides a semiconductor material and a film which have high solubility in a solvent and have high filling property, heat resistance and/or etching resistance. Further provided is a method for manufacturing a semiconductor using the semiconductor material. The present invention provides a novel compound. Providing: a semiconductor material comprising a specific aromatic hydrocarbon ring derivative, a film using the semiconductor material, and a method for producing a semiconductor. A compound comprising a specific aromatic hydrocarbon ring derivative.

Description

New compound, semiconductor material, and film and semiconductor manufacturing method using the same

Technical Field

The present invention relates to a novel compound and a semiconductor material and also to a method for producing a semiconductor by using a photolithography technique by making a film using the novel compound and semiconductor material.

Background Art

The following methods are known: a method for synthesizing a compound having monocyclic aromatic hydrocarbons linked together (Non-Patent Document 1), a method for grapheneization by linking the phenyl groups of such a compound together (Non-Patent Document 2). In addition, attempts have been made to use graphene compounds in lithium-ion secondary batteries (Patent Document 1).

In the manufacturing process of semiconductors, micro-machining is usually performed using photolithography technology using photoresists. The micro-machining process includes the following contents: a thin photoresist layer is formed on a semiconductor substrate such as a silicon wafer, the photoresist layer is covered with a mask pattern corresponding to the target device pattern, the photoresist layer is exposed to active light such as ultraviolet rays through the mask pattern, the exposed layer is developed to obtain a photoresist pattern, the obtained photoresist pattern is set as a protective film and the substrate is etched; thereby, fine concave-convex corresponding to the above-mentioned pattern is formed. The following problems arise in these photolithography processes: the dimensional accuracy of the photoresist pattern is reduced under the influence of standing waves caused by the reflection of light from the substrate or under the influence of diffuse reflection of the exposure light caused by the height difference (step difference) of the substrate. Therefore, in order to solve this problem, people are widely studying methods of setting a lower anti-reflection film. As the characteristics required for such a lower anti-reflection film, the characteristics of high anti-reflection effect are listed.

Under such circumstances, in order to reduce the reflectivity and form a pattern with high dimensional accuracy by dry etching, attempts have been made to provide a resist underlayer film containing a polymer having a specific fluorene unit (Patent Document 2). In addition, attempts have been made to provide a resist underlayer film that can reduce the reflectivity and does not cause wrinkles during etching of the substrate (Patent Document 3).

Patent Literature

Patent Document 1: Japanese Patent No. 5200523B

Patent Document 2: Japanese Patent Application Laid-Open No. 2016-81041A

Patent Document 3: Japanese Patent No. 5653880B

Non-patent document 1: Journal of Chemical and Engineering Data, James A. Harvey and Michael A. Ogliaruso. Vol. 22, No. 1, p110～(1977)

Non-patent document 2: Angew. Chem. Int. Ed. Engl. Markus Muller et al. 36 (No. 15), p1607～(1997)

Summary of the invention

Problem that the invention aims to solve

The inventors of the present invention focus on the fact that, in the photolithography process, since there are also substrates such as high-level substrates (step substrates) in the substrate before film formation, a composition that exhibits high film-forming properties even for uneven substrates is preferred. Therefore, it can be considered that it is desirable to be able to apply to a coated surface such as a substrate, and it is important that the solid component has high solubility in a solvent. In addition, in etching processes such as CVD, since heat is sometimes conducted to the surrounding layers, it can be considered that the heat resistance of the film is important, and in-depth research has been repeatedly conducted.

As a result, the inventors of the present application have successfully obtained compounds to which specific monocyclic hydrocarbons are linked. These compounds have high solubility in solvents, and when a composition containing the compounds is made into a film, the gap filling performance in fine processing structures such as grooves is excellent. In addition, the film obtained from these compositions has excellent heat resistance. In addition, it was found that these compounds have excellent etching resistance and can also be appropriately embedded in a high-low substrate, so they are suitable for use as an underlayer film.

Solutions to Solve Problems

The semiconductor material of the present invention is composed of a compound represented by the following formula (1). In the present specification, this is also referred to as "a semiconductor material represented by the formula (1)".

X-Y formula (1)

In the formula, X is a group represented by the following formula (2).

A is -OH, _-NH2 or -SH,

_R1 is hydrogen, -OH, _-NH2 , -SH, _{a C1-10} straight chain alkyl group, or _{a C3-10} branched alkyl group, or a direct bond to a phenyl ring,

R _1' is hydrogen, -OH, -NH ₂ , -SH, a C _1-10 straight chain alkyl group, or a C _3-10 branched alkyl group, or a direct bond to a phenyl ring,

_R2 is hydrogen, -OH, _-NH2 , -SH, a _C1-10 straight chain alkyl group, or a _C3-10 branched alkyl group, or a direct bond to a phenyl ring,

R _2' is hydrogen, -OH, -NH ₂ , -SH, a C _1-10 straight chain alkyl group, or a C _3-10 branched alkyl group, or a direct bond to a phenyl ring,

R ₃ is hydrogen, -OH, -NH ₂ , -SH, a C _1-10 straight chain alkyl group, or a C _3-10 branched alkyl group, or a direct bond to a phenyl ring,

R _3' is hydrogen, -OH, -NH ₂ , -SH, a C _1-10 straight chain alkyl group, or a C _3-10 branched alkyl group, or a direct bond to a phenyl ring,

n ₁ is 0, 1, or 2,

_n2 is 0, 1, or 2,

n ₃ is 0, 1, or 2,

m is 0, 1, 2, or 3, and

Y is an aromatic hydrocarbon ring group which is unsubstituted or substituted with one or more substituents, wherein the substituents are selected from -OH, -NH ₂ , -SH, a C _1-10 straight-chain alkyl group, or a C _3-10 branched alkyl group.

In addition, the composition of the present invention comprises the semiconductor material of the present invention and a solvent. In addition, the underlayer film-forming composition of the present invention comprises the composition of the present invention.

In addition, the method for producing the film of the present invention includes the following steps: laminating the composition of the present invention on a substrate and curing it. "On the substrate" in the present production method refers to "above the substrate". "Above" refers to the "upward direction", including: the case where they are laminated above in contact with each other, and the case where they are laminated via other layers. In the case where the film produced by the present production method is a lower layer film, "on the substrate" means "above the substrate and below the photoresist layer", or it can be said that it is "between the substrate and the photoresist layer". "Below" refers to the "lower direction", including: the case where they are laminated below in contact with each other, and the case where they are laminated via other layers.

For example, a substrate modification layer may be formed on the substrate in contact with the substrate, and a lower film may be manufactured on the substrate modification layer in contact with the substrate modification layer. In addition, a lower anti-reflection layer may be formed in contact with the lower film (e.g., a planarization film) of the present invention, and a photoresist layer may be formed on the lower anti-reflection layer in contact with the lower anti-reflection layer.

In addition, the semiconductor manufacturing method of the present invention includes the following steps:

Producing the lower film of the present invention,

forming a layer of photoresist composition on the lower film,

The photoresist composition is cured to form a photoresist layer.

The substrate coated with the photoresist layer is exposed to light.

The exposed substrate is developed to form a resist pattern.

The resist pattern is used as a mask for etching.

Processing the substrate.

In the process from the above-mentioned etching to the processing of the substrate, it is possible to choose to sandwich or not sandwich other etchings according to the process conditions. For example, the middle layer can be etched by etching with the resist pattern as a mask, and the substrate can be etched by using the middle layer pattern as a mask. In addition, the middle layer can be etched by etching with the resist pattern as a mask, the lower film can be etched by using the middle layer pattern as a mask, and the substrate can be etched by using the lower film pattern as a mask. Furthermore, the substrate can also be etched only by etching with the resist pattern as a mask.

In addition, the present invention provides a compound represented by the following formula (9)'.

[Chemical formula xii]

In the formula,

A is -OH, _-NH2 or -SH.

_R1 is hydrogen, -OH, _-NH2 , -SH, a _C1-10 straight chain alkyl group, or a _C3-10 branched alkyl group, or a direct bond to a phenyl ring,

R _1' is hydrogen, -OH, -NH ₂ , -SH, a C _1-10 straight chain alkyl group, or a C _3-10 branched alkyl group, or a direct bond to a phenyl ring,

_R2 is hydrogen, -OH, _-NH2 , -SH, a _C1-10 straight chain alkyl group, or a _C3-10 branched alkyl group, or a direct bond to a phenyl ring,

R _2' is hydrogen, -OH, -NH ₂ , -SH, a C _1-10 straight chain alkyl group, or a C _3-10 branched alkyl group, or a direct bond to a phenyl ring,

R ₃ is hydrogen, -OH, -NH ₂ , -SH, a C _1-10 straight chain alkyl group, or a C _3-10 branched alkyl group, or a direct bond to a phenyl ring,

R _3' is hydrogen, -OH, -NH ₂ , -SH, a C _1-10 straight chain alkyl group, or a C _3-10 branched alkyl group, or a direct bond to a phenyl ring,

n ₁ is 0, 1, or 2,

_n2 is 0, 1, or 2,

n ₃ is 0, 1, or 2,

m is 0, 1, 2, or 3,

Ar is an unsubstituted or substituted C _6-20 aromatic hydrocarbon ring. The substituent is selected from -OH, -NH ₂ , -SH, a C _1-10 straight chain alkyl group, or a C _3-10 branched alkyl group.

R _4' is hydrogen, -OH, -NH ₂ , -SH, a C _1-10 straight chain alkyl group, or a C _3-10 branched alkyl group, or a direct bond to a phenyl ring,

n ₄ is 0, 1, 2, 3, or 4,

However, the following compounds are not included:

[Chemical formula xiii]

Effects of the Invention

The compound of the present invention has high solubility in solvents, and a film formed from a composition containing the compound has excellent film-forming properties and can be embedded in a processed substrate. In addition, it was confirmed that the film has excellent heat resistance and the film thickness reduction after heating is small.

DETAILED DESCRIPTION

The above summary and the following detailed description are intended to illustrate the present invention and are not intended to limit the claimed invention.

In this specification, when "to" is used to express a numerical range, unless otherwise specified, both endpoints are included and the unit is common. For example, "5 to 25 mol%" means "5 mol% or more and 25 mol% or less".

In this specification, " _Cx-y ", " _Cx - _Cy " and " _Cx " etc. indicate the number of carbon atoms in a molecule or a substituent. For example, _C1-6 alkyl means an alkyl chain having 1 or more and 6 or less carbon atoms (methyl, ethyl, propyl, butyl, pentyl and hexyl).

In the present specification, when a polymer has a plurality of repeating units, these repeating units are copolymerized. Unless otherwise specified, these copolymerizations may be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture thereof.

In this specification, unless otherwise specified, the unit of temperature is Celsius. For example, "20 degrees" means "20 degrees Celsius".

Semiconductor Materials

The "semiconductor material" in the present invention refers to a material used in the semiconductor manufacturing process. That is, it also includes: a constituent material of a film or layer that is removed during the manufacturing process of a circuit, etc., such as a photoresist film or an underlying film. It is used in a film or layer that does not ultimately remain in the semiconductor, and this is a suitable form of the semiconductor material of the present invention. Regarding the semiconductor material, the impurities as a raw material are less than 2%, preferably less than 1%, more preferably less than 0.1%, and further preferably less than 0.01%. Regarding impurities, raw materials for the synthesis process and precursors that remain in an incompletely reacted state are listed. In the case where the semiconductor material is included in the composition, the amount of the above-mentioned impurities refers to the amount of impurities contained relative to the amount of the target semiconductor material, and the suitable amount is the same as above.

The semiconductor material in the present invention is composed of a compound represented by the following formula (1).

[Chemical formula i]

X-Y formula (1)

In the formula, X is a group represented by the following formula (2).

[Chemical formula ii]

Y is an aromatic hydrocarbon ring group which is unsubstituted or substituted with one or more substituents. The substituent is selected from -OH, _-NH2 , -SH, a _C1-10 straight-chain alkyl group, or a _C3-10 branched alkyl group. Y is preferably an unsubstituted aromatic hydrocarbon ring group, or an aromatic hydrocarbon ring group substituted with -OH or _-NH2 . The aromatic hydrocarbon ring group of Y includes monocyclic aromatic hydrocarbons, compounds of monocyclic aromatic hydrocarbons linked, and condensed aromatic hydrocarbons. For example, naphthyl substituted with two -OH substituents is also a form of Y.

A is -OH, -NH ₂ or -SH. A is preferably -OH or -NH ₂ , and A is more preferably -OH. It is believed that the A group contributes to solubility.

_R1 is hydrogen, -OH, _-NH2 , -SH, a _C1-10 straight-chain alkyl group, or a _C3-10 branched alkyl group, or a direct bond to a phenyl ring. _R1 is preferably hydrogen, -OH, _-NH2 , or a direct bond to a phenyl ring, more preferably hydrogen or a direct bond to a _phenyl ring, and even more preferably _hydrogen .

R _{1' is} hydrogen, -OH, -NH ₂ , -SH, a C _1-10 straight chain alkyl group, or a C _3-10 branched alkyl group, or a direct bond to a phenyl ring. R 1 _' is preferably hydrogen, -OH, -NH ₂ , or a direct bond to a phenyl ring, more preferably hydrogen or a direct bond to a phenyl ring, _and even more preferably hydrogen.

_R2 is hydrogen, -OH, _-NH2 , -SH, a _C1-10 straight-chain alkyl group, or a _C3-10 branched alkyl group, or a direct bond to a phenyl ring. _R2 is preferably hydrogen, -OH, _-NH2 , or a direct bond to a phenyl ring, more preferably hydrogen, -OH, or a direct bond to a _phenyl ring, further preferably _hydrogen or -OH, _and further preferably -OH.

R _{2 '} is hydrogen, -OH, -NH ₂ , -SH, a C _1-10 straight-chain alkyl group, or a C _3-10 branched alkyl group, or a direct bond to a phenyl ring. R 2 _' is preferably hydrogen, -OH, -NH ₂ , or a direct bond to a phenyl ring, more preferably hydrogen, -OH, or a direct bond to a phenyl ring, _and further preferably hydrogen or -OH.

_R3 is hydrogen, -OH, _-NH2 , -SH, a _C1-10 straight-chain alkyl group, or a _C3-10 branched alkyl group, or a direct bond to a phenyl ring. _R3 is preferably hydrogen, -OH, _{-NH2 ,} or a direct bond to a phenyl ring, more preferably hydrogen, -OH, or a direct bond to a phenyl ring, _and even more preferably hydrogen.

R _{3' is} hydrogen, -OH, -NH ₂ , -SH, a C _1-10 straight-chain alkyl group, or a C _3-10 branched alkyl group, or a direct bond to a phenyl ring. R 3 _' is preferably hydrogen, -OH, -NH ₂ , or a direct bond to a phenyl ring, more preferably hydrogen or a direct bond to a phenyl ring, _and even more preferably hydrogen.

_n1 is 0, 1 or 2. _n1 is preferably 0 or 1, and _n1 is more preferably 0.

_n2 is 0, 1 or 2. _n2 is preferably 0 or 1, and _n2 is more preferably 0.

_n3 is 0, 1 or 2. _n3 is preferably 0 or 1, and _n3 is more preferably 0.

m is 0, 1, 2 or 3. m is preferably 1, 2 or 3, and more preferably 2 or 3. When m is 2 or 3, a plurality of R ₃ , R _3′ and n ₃ are the same or different, and are preferably the same.

From the viewpoint of the synthesis route, one or two of the monocyclic aromatic hydrocarbons to which A, _R2 and/or _R3 are added are preferably bonded at the ortho position based on the bonding point with Y in the central phenyl group of formula (2) that is bonded with Y. More preferably, two monocyclic aromatic hydrocarbons are preferably bonded at the ortho position.

In formula (1), Y is preferably represented by the following formula (3), (4), (5) or (6).

[Chemical formula iii]

-L formula (3)

[Chemical formula iv]

-L-X formula (4)

[Chemical formula v]

-L-L-X formula (5)

[Chemical formula vi]

In the formula, L is a group represented by the following formula (7).

[Chemical formula vii]

(chrysene)或者并四苯，更优选为萘基或者蒽，更进一步优选为蒽。在本发明的优选的形态中，Ar是苯基或者蒽，进一步优选的形态中Ar为苯基。Ar is an unsubstituted or substituted C _6-20 aromatic hydrocarbon ring. Ar is preferably a C _6-12 aromatic hydrocarbon ring. The substituent is -OH, -NH ₂ , -SH, a C _1-10 straight _- chain alkyl group, or a C _3-10 branched alkyl group. Ar is preferably an unsubstituted C _6-20 aromatic hydrocarbon ring group, or a C _6-20 aromatic hydrocarbon ring group substituted with -OH or -NH _2. Ar is preferably a monocyclic aromatic hydrocarbon ring (phenyl, C ₆ ) or a condensed aromatic hydrocarbon ring. The condensed aromatic hydrocarbon ring is preferably naphthyl, phenalene, anthracene, phenanthrene, triphenylene, pyrene,

In a preferred embodiment of the present invention, Ar is phenyl or anthracene, and in a further preferred embodiment, Ar is phenyl.

R _{4' is} hydrogen, -OH, -NH ₂ , -SH, a C _1-10 straight-chain alkyl group, or a C _3-10 branched alkyl group, or a direct bond to a phenyl ring. R 4 _' is preferably hydrogen, -OH, -NH ₂ , or a direct bond to a phenyl ring, more preferably hydrogen, -OH, or a direct bond to a _phenyl ring, and further preferably hydrogen or -OH.

n ₄ is 0, 1, 2, 3 or 4. Preferably, n ₄ is 0 or 1, and more preferably 0. When n ₄ is plural (2, 3 or 4), there are plural phenyl groups of formula (7) to which R _4' is given, and each of them is bonded to Ar, or is bonded to other phenyl groups via a phenyl group as in biphenyl, which is a preferred form. When n ₄ is plural, each phenyl group in the phenyl group of formula (7) to which R _4' is given is bonded to Ar as in the following left compound, which is a more preferred form. As an example of a compound bonded to other phenyl groups via a phenyl group as another form, the following right compound is listed.

[化学式xv]

[Chemical formula xiv]

[Chemical formula xv]

In formula (3), (4), (5) or (6), the binding points at which L binds to one or more Xs are respectively supplied from Ar. In formula (5), the binding points at which L binds to another L are respectively supplied from Ar. The definition and preferred form of X are the same as above. Here, the multiple Xs in formula (1) are the same or different from each other, preferably the same. Y is represented by formula (4), which is a preferred form of the present semiconductor material.

Regarding the compounds of formula (4), (5) or (6), when they are symmetrical compounds, they have the advantage of fewer synthesis steps, and when they are asymmetrical, the film formed becomes amorphous, which has the advantage of further improving heat resistance. Regarding the compound of formula (4), a structure with L (more preferably Ar) between two Xs as the central axis and left-right symmetry or left-right asymmetry can be adopted. Regarding the compound of formula (5), a structure with the center of two Ls as the axis and left-right symmetry or left-right asymmetry can be adopted. Regarding the compound of formula (6), a structure with L (more preferably Ar) between three Xs as the central point and point symmetry or point asymmetry can be adopted.

The number of carbon atoms in the compound of the formula (1) of the present invention as a whole is preferably 42-120, more preferably 50-100, further preferably 60-90, and further preferably 66-84.

One preferred embodiment of L is a group represented by the following formula (12).

[Chemical formula xvi]

At least one of _P1 and _P2 surrounded by the dotted line forms an aromatic hydrocarbon ring condensed with an adjacent phenyl group, or _P1 and _P2 form nothing. The definitions and/or preferred forms of _R4' and _n4 are the same as above. The aromatic hydrocarbon ring containing _P1 or _P2 as a whole conforms to Ar of formula (7). Therefore, the position at which the phenyl group to which R4 _' is given is bound to the aromatic hydrocarbon ring is not limited to the phenyl group, but may also be the _P1 or _P2 ring. The position at which the phenyl group to which R4 _' is given is preferably bound to the phenyl group to which _P1 or _P2 is given. The same is true for the formulas (16), (18) and (20) described later.

For example, the lower left group is a form of L, _P1 and _P2 are both phenyl rings and condense with adjacent phenyl groups to form an anthracene ring as a whole. In addition, the lower right group is a form of L, _P1 and _P2 are nothing. In both the lower left group and the lower right group, R _4' is hydrogen and n ₄ is 1.

[Chemical formula xvii]

The compound of formula (1) is preferably represented by formula (8), (9), (10) or (11).

[Chemical formula viii]

[Chemical formula ix]

[Chemical formula x]

[Chemical formula xi]

In formulae (8), (9), (10) and (11), the definitions and preferred aspects of A, R ₁ , R _1′ , R ₂ , R _2′ , R ₃ , R _3′ , n ₁ , n ₂ , n ₃ , m, Ar, R _4′ , and n ₄ are each independently the same as described above.

In formulae (8), (9), (10) and (11), when there are plural A, R ₁ , R _1′ , R ₂ , R _2′ , R ₃ , R _3′ , n ₁ , n ₂ , n ₃ , m, Ar, R _4′ , and n ₄ , the plural ...

In the present application, the "direct bond to the phenyl ring" in R ₁ , R _1' , R ₂ , R _2' , R ₃ , R _3' , and R ₄ means that the phenyl groups in formula (2) are directly bonded to each other without being bonded via other connecting groups. That is, the "direct bond to the phenyl ring" does not include a form in which the phenyl rings are bonded to each other via an alkylene group, such as at position 9 of fluorene. In addition, the direct bond to the phenyl ring improves the planarity of the molecule of formula (1).

For example, regarding the following compound represented by formula (1), Y is formula (4) (-LX), and A in formula (2) is -OH. The phenyl group to which A is given is bonded to L (phenyl) at the ortho position. R ₁ , R ₃ , R _1' , R _2' and R _3' are hydrogen, m is 3, and n ₁ , n ₂ and n ₃ are 0. R ₂ is a direct bond to the phenyl ring. Ar in formula (7) is unsubstituted phenylene (C ₆ ), R _4' is hydrogen, and n ₄ is 0. The two Xs are the same.

[Chemical formula xviii]

The compound of formula (1) is more preferably represented by formula (13), (14), (15), (16), (17), (18), (19) or (20).

[Chemical formula xix]

[Chemical formula xx]

[Chemical formula xxi]

[Chemical formula xxii]

[Chemical formula xxiii]

[Chemical formula xxiv]

[Chemical formula xxv]

[Chemical formula xxvi]

In formulae (13), (14), (15), (16), (17), (18), (19) and (20), the definitions and/or preferred aspects of A, R ₁ , R _1′ , R ₂ , R _2′ , R ₃ , R _3′ , n ₁ , n ₂ , n ₃ , m, Ar, R _4′ , n ₄ , P ₁ and P ₂ are each independently the same as described above.

In formulae (13), (14), (15), (16), (17), (18), (19) and (20), when there is a plurality of A, R ₁ , R _1' , R ₂ , R _2' , R ₃ , R _3' , n ₁ , n ₂ , n ₃ , m, Ar, R _4' , n ₄ , P ₁ and P ₂ , the plurality of them may be the same or different from each other, and are preferably the same.

A more preferred embodiment of the compound of formula (1) is a compound represented by formula (15).

The compound represented by formula (1) has a high carbon content as a whole due to the linking of a monocyclic aromatic hydrocarbon, and further has an A group. This is considered to provide the following properties useful as a semiconductor material, namely, high etching resistance as a whole and high solubility in a solvent.

For the purpose of explanation, specific examples of the compound represented by formula (1) are shown below, but are not intended to limit the present invention.

[Chemical formula xxvii]

Method for synthesizing semiconductor material of formula (1)

Regarding the synthesis method of the semiconductor material of formula (1), the specific form is recorded in the synthesis example of the embodiment described later. In addition, regarding the above-mentioned semiconductor material, the A group of the semiconductor material of the present application is added to the precursor or synthetic material described in non-patent document 1, non-patent document 2 and patent document 1 to obtain it. Furthermore, as in the synthesis example of the present application, by synthesizing an intermediate with a methoxy group added, the methoxy group is replaced by the A group, thereby obtaining the semiconductor material of the present application.

The semiconductor material of formula (8) can be synthesized by the following synthesis method. Cyclopentane-2,4-dienone reacts with acetylene to form the central phenyl group of X. A substituent (eg, a phenyl group with a subscript m outside the brackets) can be given to the central phenyl group of X by further adding a substituent to the acetylene.

[Chemical formula xxviii]

Semiconductor materials of formula (9), (10) and (11) can be synthesized by using the above-mentioned synthesis route and changing the intermediate or the amount. As in the following synthesis route, the compound of formula (9) can be obtained by changing the number of acetylene given to Ar to two and reacting twice the amount of X.

[Chemical formula xxix]

Similarly, by setting the number of acetylene given to Ar to three and reacting three times the amount of X, the compound of formula (11) can be obtained.

The compound of formula (10) can be obtained by using the following compound as the intermediate and reacting 2 times the amount of X.

[Chemical formula xxx]

Composition

The composition of the present invention comprises a semiconductor material of formula (1) and a solvent.

The semiconductor material of formula (1) contained in the composition is not limited to a single compound as long as it is represented by formula (1), and may be a combination of a plurality of compounds. For example, the following two compounds may both be contained in the present composition.

[Chemical formula xxxi]

In the case of this combination, these compounds may be combined during film formation or may be combined individually. From the viewpoint of production handling, the compound of formula (1) contained in the present composition is preferably a single compound.

The amount of the semiconductor material of formula (1) is preferably 2 to 40% by mass, more preferably 2 to 30% by mass, further preferably 2 to 20% by mass, and further preferably 3 to 10% by mass compared to the entire composition. A thick film can be formed by increasing the amount of solid components in the entire composition.

Solid components other than the semiconductor material of formula (1)

The planarized film-forming composition of the present invention may further include a solid component for film formation in addition to the semiconductor material of formula (1). Such a solid component may be a low molecular weight compound (including a monomer) different from the semiconductor material of formula (1) or a polymer. When film formation occurs, these solid components may be combined with the semiconductor material of formula (1), may be combined individually, or may exist in a mixed state.

Solvents

Examples of the present solvent include water and organic solvents.

As for the organic solvent, for example, aliphatic hydrocarbon solvents such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, n-pentylnaphthalene, and trimethylbenzene; and methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutyl alcohol, sec-butanol, tert-butanol, n-pentanol, isopentyl alcohol, and isopentyl alcohol. Monohydric alcohol solvents such as alcohol, 2-methylbutanol, secondary amyl alcohol, tert-amyl alcohol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, secondary hexanol, 2-ethylbutanol, secondary heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, secondary octanol, n-nonanol, 2,6-dimethyl-4-heptanol, n-decanol, secondary undecyl alcohol, trimethyl nonanol, secondary tetradecanol, secondary heptadecanol, phenol, cyclohexanol, methyl cyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, cresol, etc.; ethylene glycol, propylene glycol, 1,3-Butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol and other polyol solvents; acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, trimethyl nonanone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2,4-pentanediol Ketone solvents such as acetone, acetone alcohol, acetophenone, and fenchone; ethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyl dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol Ether solvents such as alcohol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriethylene glycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran; diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone , γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate Acid esters, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, ethylene glycol diacetate, methoxytriethylene glycol acetate, ethyl propionate, n-butyl propionate, isopentyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate (EL), γ-butyrolactone, n-butyl lactate, n-pentyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, propylene glycol 1-monobutyl Ester solvents such as methyl ether 2-acetate (PGMEA), propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; nitrogen-containing solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and N-methylpyrrolidone; sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propane sultone. Alternatively, a mixed solution thereof may be used.

In particular, from the viewpoint of storage stability of the solution, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol 1-monomethyl ether 2-acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, γ-butyrolactone, ethyl lactate, or a mixture thereof is preferred.

From the viewpoint of solubility of the solute, propylene glycol monomethyl ether, propylene glycol 1-monomethyl ether 2-acetate, ethyl lactate, or a mixture of two of them is preferred. The two mixtures are preferably a mixture in a volume ratio of 10:90 to 90:10, and more preferably a mixture in a volume ratio of 25:75 to 75:25.

Compared with the whole composition, the amount of one or more solvents (the sum of them in multiple cases) is preferably 60 to 98% by mass, more preferably 70 to 98% by mass, and further preferably 80 to 98% by mass. The solvent is preferably an organic solvent, and the amount of water in the composition is preferably 0.1% by mass or less, and further preferably 0.01% by mass or less. Because of the relationship with other layers or films, the solvent preferably does not contain water, and the amount of water in the composition is 0.00% by mass, which is one form of the present invention.

Surfactants

The present composition may further contain a surfactant, a crosslinking agent, an acid generator, a free radical generating material, a substrate adhesion enhancer, or a mixture thereof.

The surfactant is useful for suppressing the generation of pinholes and striations, and improving coating properties and solubility. The amount of the surfactant in the present composition is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, based on the entire composition.

As surfactants, there are listed polyoxyethylene alkyl ether compounds such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether, polyoxyethylene alkyl allyl ether compounds such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene-polyoxypropylene block copolymer compounds, sorbitan fatty acid ester compounds such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan trioleate and sorbitan tristearate, and polyoxyethylene sorbitan fatty acid ester compounds such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate and polyoxyethylene sorbitan tristearate. In addition, fluorine-based surfactants such as trade names EFTOP EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), trade names Megafac F171, F173, R-08, R-30, R-2011 (manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Limited), trade names AsahiGuard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be mentioned.

Crosslinking agent

The crosslinking agent may be added for the purpose of improving the film-forming property of the formed film, eliminating intermixing with upper films such as the silicon-containing intermediate layer and the resist layer, and eliminating diffusion of low molecular components into the upper film.

When enumerating specific examples of the crosslinking agent that can be used in the present invention, melamine compounds, guanamine compounds, glycoluril compounds or urea compounds, epoxy compounds, thioepoxy compounds, isocyanate compounds, azide compounds, compounds having a group containing a double bond such as an alkenyl ether group, which are substituted with at least one group selected from hydroxymethyl, alkoxymethyl, and acyloxymethyl groups can be listed. These can also be used as additives, but can also be introduced into the polymer side chain as a pendant group. In addition, compounds containing a hydroxyl group are also used as crosslinking agents.

Examples of epoxy compounds among the above compounds include tris(2,3-epoxypropyl)isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, triethylolethane triglycidyl ether, etc. Specific examples of melamine compounds include hexamethylolmelamine, hexamethoxymethylmelamine, compounds obtained by methoxymethylating 1 to 6 methylol groups in hexamethylolmelamine, and mixtures thereof, hexamethoxyethylmelamine, hexaacyloxymethylmelamine, compounds obtained by acyloxymethylating 1 to 6 methylol groups in hexamethylolmelamine, and mixtures thereof. As for the guanamine compounds, tetramethylolguanamine, tetramethoxymethylguanamine, compounds obtained by methoxymethylating 1 to 4 hydroxymethyl groups of tetramethylolguanamine, and mixtures thereof, tetramethoxyethylguanamine, tetraacyloxyguanamine, compounds obtained by acyloxymethylating 1 to 4 hydroxymethyl groups of tetramethylolguanamine, and mixtures thereof are listed. As for the glycoluril compounds, tetramethylolglycouril, tetramethoxyglycouril, tetramethoxymethylglycouril, compounds obtained by methoxymethylating 1 to 4 hydroxymethyl groups of tetramethylolglycouril, or mixtures thereof, compounds obtained by acyloxymethylating 1 to 4 hydroxymethyl groups of tetramethylolglycouril, or mixtures thereof are listed. As for the urea compounds, tetramethylolurea, tetramethoxymethylurea, compounds obtained by methoxymethylating 1 to 4 hydroxymethyl groups of tetramethylolurea, or mixtures thereof, and tetramethoxyethylurea are listed.

Examples of the compound containing an alkenyl ether group include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propylene glycol divinyl ether, 1,4-butylene glycol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether and trimethylolpropane trivinyl ether.

Examples of the crosslinking agent of the present invention include a crosslinking agent represented by the following formula (21).

[Chemical formula xxxii]

In formula (21), _L3 is a direct bond, a substituted or unsubstituted _C1-3 alkyl group, or a substituted or unsubstituted _C7-16 aralkyl group. _L3 is preferably a direct bond, a _C1 alkyl group, or a _C15 aralkyl group. The substituent of the alkyl group or aralkyl group is preferably hydrogen, a methyl group, a _C6-11 aryl group, the following formula (22) or the following formula (23), and more preferably a methyl group or the following formula (22). It is also a preferred embodiment that the _C1-3 alkyl group or the _C7-16 aralkyl group of _L3 is unsubstituted.

[Chemical formula xxxiii]

[Chemical formula xxxiv]

In the formula (21), specific examples of the cross-linking agent represented by the formula (21) in which R ₁₁ is hydrogen or methyl are as follows, but the scope of the present invention is not limited thereto.

[Chemical formula xxxv]

Specific examples of other crosslinking agents that may be contained in the planarizing film-forming composition are as follows, but the scope of the present invention is not limited to these.

[Chemical formula xxxvi]

These crosslinking agents can also be obtained from Sanwa Chemical Co., Ltd., Honshu Chemical Industry Co., Ltd., Asahi Yukizai Corporation, Nippon Carbide Industries Co., Inc., and the like.

The amount of the crosslinking agent in the present invention is preferably 10 to 100% by mass, more preferably 40 to 100% by mass, further preferably 50 to 90% by mass, and further preferably 70 to 90% by mass, compared to the mass of the semiconductor material of formula (1) contained in the present composition (or the sum of the semiconductor materials in the case of a plurality of semiconductor materials). It is expected that the inclusion of the crosslinking agent in the composition will have the following effect: since the crosslinking agent is bonded to the compound of formula (1) during film formation, the combination of the crosslinking agent and the compound of formula (1) as a whole improves planarity by controlling the intramolecular torsion.

From the viewpoint of process management, it is also one aspect of the present invention to form a film using only the semiconductor material of formula (1) without adding a crosslinking agent (0 mass % compared to the mass of the semiconductor material of formula (1)).

Acid Generator

The composition of the present invention may further contain an acid generator. The amount of the acid generator contained in the composition is preferably 0.1 to 10% by mass, more preferably 1 to 7% by mass, and even more preferably 1 to 5% by mass, compared to the mass of the semiconductor material of formula (1) (or the sum of the mass of the semiconductor materials of formula (1) in the case of a plurality of semiconductor materials of formula (1)).

Regarding the acid generator, it can be set as a thermal acid generator that can generate a strong acid by heating. Regarding the thermal acid generator (TAG) used in the present invention, it can be any one or more thermal acid generators that generate the following acids by heating, and the acid is an acid that can react with the semiconductor material of formula (1) present in the present invention and can transmit the crosslinking of the semiconductor material, and is more preferably a strong acid such as sulfonic acid. Preferably, regarding the thermal acid generator, it is activated at a temperature exceeding 80 degrees. Examples of thermal acid generators are: metal-free sulfonium salts and iodonium salts, for example, triarylsulfonium, dialkylarylsulfonium, and diarylalkylsulfonium salts of strong non-nucleic acid affinity, alkylaryliodonium, diaryliodonium salts of strong non-nucleic acid affinity; and ammonium, alkylammonium, dialkylammonium, trialkylammonium, and tetraalkylammonium salts of strong non-nucleic acid affinity. In addition, covalent thermal acid generators are also considered as useful additives, such as 2-nitrobenzyl esters of alkylsulfonic acids or arylsulfonic acids, and other esters of sulfonic acids that produce free sulfonic acids after thermal decomposition. Examples thereof are: diaryliodonium perfluoroalkylsulfonates, diaryliodonium tris(fluoroalkylsulfonyl)methides, diaryliodonium bis(fluoroalkylsulfonyl)methides, diaryliodonium bis(fluoroalkylsulfonyl)imides, diaryliodonium quaternary ammonium perfluoroalkylsulfonates. Examples of unstable esters are: 2-nitrobenzyl p-toluenesulfonate, 2,4-dinitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, 4-nitrobenzyl p-toluenesulfonate; benzenesulfonates such as 2-trifluoromethyl-6-nitrobenzyl-4-chlorobenzenesulfonate and 2-trifluoromethyl-6-nitrobenzyl-4-nitrobenzenesulfonate; phenolic sulfonates such as phenyl 4-methoxybenzenesulfonate; quaternary ammonium tris(fluoroalkylsulfonyl)methylates and quaternary alkylammonium bis(fluoroalkylsulfonyl)imides, alkylammonium salts of organic acids, for example, triethylammonium salt of 10-camphorsulfonic acid. Various aromatic (anthracene, naphthalene, or benzene derivative) sulfonic acid amine salts including those disclosed in U.S. Patent Nos. 3,474,054 (Patent Document 4), 4,200,729 (Patent Document 5), 4,251,665 (Patent Document 6), and 5,187,019 (Patent Document 7) can be used as TAG.

Specific examples of the thermal acid generator that may be contained in the present composition are as follows, but the scope of the present invention is not limited thereto.

[Chemical formula xxxvii]

From the viewpoint of process management, it is also one embodiment of the present invention that no acid generator is added to the composition (0 mass % compared to the mass of the semiconductor material of formula (1)).

Free Radical Generators

In the present composition, a free radical generator may be added to initiate polymerization. The free radical generator is a reagent that generates free radicals by heating, and examples thereof include azo compounds and peroxides. Specific examples thereof include hydroperoxides such as diisopropylbenzene hydroperoxide, cumene hydroperoxide, and tert-butyl hydroperoxide, α,α-bis(tert-butylperoxy-m-isopropyl)benzene, diisopropylbenzene peroxide (dicumyl hydroperoxide, etc.), and diisopropylbenzene peroxide (dicumyl hydroperoxide). Peroxide), 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)3-hexyne, tert-butyl peroxy-2-ethylhexanoate and other dialkyl peroxides, ketone peroxides, peroxyketals such as 4,4-di-(tert-butylperoxy)valerate and other n-butyl peroxides, diacyl peroxides, peroxydicarbonates, peroxyesters and other organic peroxides, and azo compounds such as 2,2'-azobisisobutylnitrile, 1,1'-azo(cyclohexane-1-carbonitrile), 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis(2,4-dimethylvaleronitrile) and the like. These thermal free radical generators may be used alone or in combination, and are preferably used alone. These known free radical generators can be used in the present composition, and these free radical generators are available from, for example, NOFCORPORATION.

From the viewpoint of process management, no radical generator is added to the present composition (0 mass % compared to the mass of the semiconductor material of formula (1)), which is also one aspect of the present invention.

Other ingredients

The composition of the present invention may further contain other ingredients such as a substrate adhesion enhancer, a smoothing agent, a monomeric dye, a lower alcohol (C _1-6 alcohol), a surface leveling agent, a defoaming agent, and a preservative. The amount of these ingredients in the composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, compared to the semiconductor material of formula (1) in the composition. It is also an aspect of the present invention that the composition does not contain these ingredients (0% by mass).

Lower film forming composition

The composition of the present invention is useful as a composition for forming a lower film, for example, for the manufacture of patterns using photolithography. In etching technology, films (also referred to as layers) for various purposes are used to form fine patterns, but the composition is advantageous for the use of these films due to its good film-forming properties and embedding characteristics.

The lower film refers to a film formed between the substrate and the photoresist layer, and includes a planarization film, a close-contact layer, and a lower anti-reflection layer (BARC layer). The lower film may also have their functions, for example, it may also function as both a planarization film and a BARC layer. The lower film forming composition is a composition for forming the lower film. A suitable form of the lower film is a planarization film, and a suitable form of the lower film forming composition is a planarization film forming composition.

The flattening film forming composition in the present invention refers to a composition that forms a film between a substrate and a photoresist film and makes the upper surface of the film (facing the photoresist layer side) have high flatness. Preferably, an intermediate layer (a Si-containing anti-corrosion intermediate layer, a close-contact layer, a lower anti-reflection film, or a combination thereof) can also be formed on the upper side of the flattening film (facing the photoresist layer side), and a photoresist layer is formed thereon. Regarding the substrate in the present invention, considering the height of the etching tolerance of the present composition and the ease of handling, it can also be a flat substrate, but considering the excellent embedding characteristics of the present composition, its effect is fully exerted even for an uneven substrate.

In addition, since the semiconductor material has high heat resistance, etching resistance and filling properties, the planarization film can also be effectively used as a hard mask layer. Since the hard mask layer is formed thickly (e.g., 1,000 to 3,000 nm), the small amount of film thickness reduction caused by heat is useful for not generating strain in the film. In addition, the etching resistance is required to be higher than that of the usual planarization film and spin-on carbon film (SOC film). One suitable form of the planarization film forming composition is a hard mask layer forming composition.

Method for manufacturing planarizing film

One embodiment of the method for forming the planarizing film of the present invention will be described. It should be noted that the film forming method and conditions described below are also applicable to the film formed from the present composition and the underlayer film of the present invention.

As described above, the present flattening film-forming composition refers to a composition that forms a film between a substrate and a photoresist film and makes the upper surface of the film (the side facing the photoresist layer) have high flatness. High flatness means that the upper surface of the flattening film is formed horizontally. In addition, as long as the flatness is high, the deviation in the distance between the bottom surface of the horizontally set substrate (the bottom substrate when multiple substrates are stacked) and the upper surface of the flattening film becomes smaller. "Flat substrate" means that the distance between the bottom surface of the substrate and the upper surface of the substrate is substantially equal (the difference in this distance within the substrate is 0 to 3%).

"Uneven substrate" refers to a substrate that is not a flat substrate in a broad sense. In the present invention, as for the uneven substrate, there are listed a height difference substrate and a concave-convex substrate. As an uneven substrate, a metal-containing substrate in which the height difference between the top and the bottom of the surface of the substrate is 10 to 10,000 nm, preferably 50 to 1,000 nm, and more preferably 100 to 1,000 nm is listed. Furthermore, as for the uneven substrate, a substrate having walls and/or contact holes due to pretreatment is listed. The above-mentioned walls and/or contact holes can be formed by known techniques such as photolithography, etching, DSA, etc., and the aspect ratio is preferably 10 to 100 (preferably 25 to 75). Furthermore, the flat film-forming composition of the present invention can also be applied to substrates with height differences. The height difference is preferably 10 to 10,000 nm, more preferably 50 to 1,000 nm, and more preferably 100 to 1,000 nm.

The planarizing film of the present invention can be formed into a film with a thickness of 20 to 3,000 nm (preferably 100 to 2,000 nm, more preferably 200 to 400 nm) by applying the film onto a planarized substrate (bare wafer) and heating the film.

Regarding the substrate, a flat substrate as well as an uneven substrate can be used as described above.

The substrate may be a metal-containing substrate or a silicon-containing substrate. The substrate in the present invention may be a single substrate or a multilayer substrate comprising a plurality of substrate layers. In terms of the substrate, known substrates such as a silicon-coated substrate, a silicon dioxide-coated substrate, a silicon nitride substrate, a silicon wafer substrate ( _SiO2 wafer, etc.), a glass substrate, an indium-containing substrate (ITO substrate, etc.), a titanium-containing substrate (titanium nitride, titanium oxide, etc.) may be used.

In the semiconductor manufacturing process of the present invention, the substrate layer structure can be formed by using a known technique according to the process conditions, but the following stacked structures are exemplified. In the following stacked structures, left indicates the downward direction, and right indicates the upward direction.

Silicon wafer substrate

Silicon wafer substrate/Titanium-containing substrate

Silicon wafer substrate/Titanium-containing substrate/Silicon-coated substrate

Silicon wafer substrate/Titanium-containing substrate/Silicon dioxide-coated substrate

Silicon wafer substrate/Silicon dioxide coated substrate/Titanium containing substrate

Silicon Nitride Substrate

Silicon nitride substrate/Titanium-containing substrate

Silicon nitride substrate/Titanium-containing substrate/Silicon-coated substrate

Silicon nitride substrate/Titanium-containing substrate/Silicon dioxide-coated substrate

Silicon nitride substrate/Silicon dioxide coated substrate/Titanium containing substrate

The other substrates stacked on any one of the substrates can be stacked using a known technique such as a CVD method. The other substrates can be patterned using a known etching technique and/or etching technique. On the patterned substrate, other substrates can also be stacked using a known technique such as a CVD method.

In the present invention, the present composition is laminated on a substrate. Lamination can be performed by a known method, preferably coating. Coating can be performed by a known method such as a spinner, a coater, etc. In terms of coating the present composition on a substrate, the so-called substrate means that it is appropriate for the substrate to be in direct contact with the present composition, but it can also be coated via other thin films (e.g., substrate modification layers). After coating the present composition, a film is formed by heating. As heating conditions, the heating temperature is appropriately selected from the range of 150 to 650° C. (preferably 200 to 650° C., more preferably 250 to 600° C.), and the heating time is generally appropriately selected from the range of 30 to 180 seconds (preferably 30 to 120 seconds). The present semiconductor material has high heat resistance, so even if it is heated at 400 to 500° C. for 0.5 to 8 hours, the reduction in film thickness is small. The heating may be performed in multiple steps (step baking). For example, the heating may be performed in two steps. The first heating is used to remove the solvent and embed the film toward the substrate. The second heating is used to gently reflux the film to ensure flatness and form a film. For example, it is also preferred to perform the first heating at 200 to 300°C for 30 to 120 seconds and the second heating at 300 to 650°C for 30 to 120 seconds. The heating atmosphere may be air, but the oxygen concentration may be reduced to prevent oxidation of the present planarizing film composition and the present planarizing film. For example, the oxygen concentration may be set to 1,000 ppm or less (preferably 100 ppm or less) by injecting an inert gas ( _N2 , Ar, He or a mixture thereof) into the atmosphere.

Since the present film contains the semiconductor material of formula (1), the carbon content of the film composition is high and the etching rate is low, so it is preferably used as a flattening film formed by a spin-on coating method. The etching rate can be evaluated using known techniques, and preferably, for example, a film having an etching rate of 1.0 or less obtained by comparison with a resist film (UV1610, Dow Chemical Company system), more preferably a film of 0.9 or less, and further preferably a film of 0.8 or less.

Regarding the film-forming form of the composition of the present invention, a form in which the solid component is layered after the solvent is removed is listed. As another film-forming form, a form in which a plurality of solid components are combined is listed. Regarding the combination of solid components, it is not limited to the state in which all the molecules of the solid components in the composition are combined, and also includes a form in which a part of them are combined.

Formation of photoresist film and other films

On the film thus formed, a photoresist composition (e.g., a positive photoresist composition) is applied. The film formed by the present composition above the substrate and below the photoresist film is the lower film. A positive photoresist composition refers to a composition that triggers a reaction by light irradiation, thereby increasing the solubility of the irradiated portion relative to the developer. The photoresist composition used is not particularly limited, but any positive photoresist composition, negative photoresist composition, or negative tone developing (NTD) photoresist composition can be used as long as it is sensitive to the exposure light used in pattern formation.

In the method for manufacturing the resist pattern of the present invention, it is also allowed to have a film or layer other than the lower film and the photoresist film formed by the present composition. It is also possible to sandwich an intermediate layer in a state where the lower film is not directly in contact with the photoresist film. The intermediate layer is a film formed between the photoresist film and the present lower film, and examples thereof include a lower anti-reflective film (BARC layer), an inorganic hard mask intermediate layer (silicon oxide film, silicon nitride film, and silicon oxynitride film), and a close-contact film. Regarding the formation of the inorganic hard mask intermediate layer, reference may be made to Japanese Patent No. 5336306 (Patent Document 8). The intermediate layer may be composed of one layer or multiple layers. In addition, an upper anti-reflective film (TARC layer) may also be formed on the photoresist film.

In the semiconductor manufacturing process of the present invention, regarding the layer structure other than the underlying film, a known technique can be used in accordance with the process conditions, and the following stacked structure is exemplified.

Substrate/underlayer film/photoresist film

Substrate/planarization film/BARC layer/photoresist film

Substrate/planarization film/BARC layer/photoresist film/TARC layer

Substrate/planarization film/inorganic hard mask intermediate layer/photoresist film/TARC layer

Substrate/planarization film/inorganic hard mask intermediate layer/BARC layer/photoresist film/TARC layer

Substrate/planarization film/adhesive film/BARC layer/photoresist film/TARC layer

Substrate/substrate modification layer/planarization film/BARC layer/photoresist film/TARC layer

Substrate/Substrate modification layer/Planarization film/Adhesion film/BARC layer/Photoresist film/TARC layer

These layers can be formed by curing by heating and/or exposure after coating, or by using a known technique such as CVD. These layers can be removed by a known technique (etching, etc.), and can be patterned using the upper layer as a mask.

The film formed from the present composition is preferably an underlayer film, more preferably a planarization film or a BARC layer, and further preferably a planarization film. The film formed from the present composition is not preferably used as an inorganic hard intermediate layer.

As one aspect of the present invention, this lower film can be formed on an uneven substrate, and another substrate can be formed thereon. For example, another substrate can be formed by methods such as CVD. The lower substrate and the upper substrate can have the same composition or different compositions. Another layer can be further formed on the upper substrate. Regarding this other layer, the upper substrate can be processed by forming this lower film and/or a photoresist film. The photoresist film or other films that can be used are the same as those described above.

Patterning, device manufacturing

The photoresist film is exposed through a predetermined mask. The wavelength of the light used in the exposure is not particularly limited, but it is preferably exposed using light with a wavelength of 13.5 to 248 nm. Specifically, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), and ultrashort ultraviolet light (wavelength 13.5 nm) can be used, and KrF excimer laser is more preferred. These wavelengths allow a range of ±1%. After exposure, post-exposure heating may also be performed as needed. The temperature for post-exposure heating is appropriately selected from 80 to 150°C, preferably appropriately selected from 100 to 140°C, and the heating time is appropriately selected from 0.3 to 5 minutes, preferably appropriately selected from 0.5 to 2 minutes.

Next, development is performed using a developer. When a positive photoresist composition is used, the exposed portion of the positive photoresist layer is removed by development to form a photoresist pattern. This photoresist pattern can be further miniaturized by using a shrink material or the like.

As the developer used in the development in the above-mentioned photoresist pattern forming method, a 2.38 mass % TMAH aqueous solution is preferably used. By using such a developer, the planarization film can be easily dissolved and removed at room temperature. Furthermore, a surfactant or the like can also be added to these developers. The temperature of the developer is generally appropriately selected from 5 to 50° C., preferably appropriately selected from 25 to 40° C., and the development time is generally appropriately selected from 10 to 300 seconds, preferably appropriately selected from 30 to 60 seconds.

The obtained photoresist pattern can be used as a mask to pattern the intermediate layer, the lower film and/or the substrate. In terms of pattern formation, known techniques such as etching (dry etching, wet etching) can be used. For example, the intermediate layer can be etched by setting the photoresist pattern as an etching mask, and the planarization film and the substrate can be etched by setting the obtained intermediate layer pattern as an etching mask, thereby forming a pattern in the substrate. As another form, the inorganic hard mask intermediate layer can be etched by setting the photoresist pattern as an etching mask, the inorganic hard mask intermediate layer pattern can be etched by setting the obtained inorganic hard mask intermediate layer pattern as an etching mask, and the planarization film can be etched by setting the obtained planarization film pattern as an etching mask, thereby forming a pattern in the substrate. In addition, the layer below the photoresist layer (such as the intermediate layer and/or the lower film) can be etched by setting the photoresist pattern as an etching mask, and the substrate can be etched as it is. The formed pattern can be used to form wiring on the substrate.

For example, the present underlayer film can be preferably removed by dry etching using O ₂ , CF ₄ , CHF ₃ , Cl ₂ or BCl ₃ , and O ₂ or CF ₄ can be preferably used.

Thereafter, the substrate is further processed as required to form a device. The further processing thereof can be applied to a known method. After the device is formed, the substrate is cut into chips as required, connected to a lead frame, and packaged with a resin. In the present invention, the product obtained by this package is called a semiconductor.

Novel compound and method for synthesizing the same

The present invention provides a novel compound represented by the following formula (9)'.

[Chemical formula xii]

In the formula,

A is -OH, _-NH2 or -SH,

_R1 is hydrogen, -OH, _-NH2 , -SH, a _C1-10 straight chain alkyl group, or a _C3-10 branched alkyl group, or a direct bond to a phenyl ring,

R _1' is hydrogen, -OH, -NH ₂ , -SH, a C _1-10 straight chain alkyl group, or a C _3-10 branched alkyl group, or a direct bond to a phenyl ring,

_R2 is hydrogen, -OH, _-NH2 , -SH, a _C1-10 straight chain alkyl group, or a _C3-10 branched alkyl group, or a direct bond to a phenyl ring,

R _2' is hydrogen, -OH, -NH ₂ , -SH, a C _1-10 straight chain alkyl group, or a C _3-10 branched alkyl group, or a direct bond to a phenyl ring,

R ₃ is hydrogen, -OH, -NH ₂ , -SH, a C _1-10 straight chain alkyl group, or a C _3-10 branched alkyl group, or a direct bond to a phenyl ring,

R _3' is hydrogen, -OH, -NH ₂ , -SH, a C _1-10 straight chain alkyl group, or a C _3-10 branched alkyl group, or a direct bond to a phenyl ring,

n ₁ is 0, 1, or 2,

_n2 is 0, 1, or 2,

n ₃ is 0, 1, or 2,

m is 0, 1, 2, or 3,

Ar is a C _6-20 aromatic hydrocarbon ring,

R _4′ is hydrogen, —OH, —NH ₂ , —SH, a C _1-10 straight chain alkyl group, or a C _3-10 branched alkyl group, or a direct bond to a phenyl ring, and

n ₄ is 0, 1, 2, 3, or 4,

However, the following compounds are excluded from formula (9)':

[Chemical formula xiii]

Regarding the above formula (9)', except for excluding the compound represented by [chemical formula xiii], the compound is the same as the semiconductor material of formula (9). The preferred form is also the same as the form described above in formula (9). Since formula (15) and formula (16) are subordinate concepts of formula (9), as a preferred example of formula (9)', a compound obtained by excluding the compound represented by chemical formula 13 from the compounds of the semiconductor materials of formulas (15) and (16) is listed.

The compound represented by formula (9)' is not a precursor in the middle of a synthetic route, but can be used as such. For example, it can be used in a photolithography process in semiconductor manufacturing.

The compound represented by the formula (9)' can be produced by the same method as that for the semiconductor material compound of the above-mentioned formula (9).

Example

Hereinafter, the present invention will be described using specific examples. These examples are for illustration and are not intended to limit the scope of the present invention. It should be noted that, in the following, unless otherwise specified, "parts" are based on mass.

Synthesis Example 1 of G1

A reactor equipped with a stirrer, a condenser (Liebig condenser), a heating device, a nitrogen inlet pipe, and a temperature control device was prepared. 3,4-bis(4-methoxyphenyl)-2,5-diphenylcyclopenta-2,4-dienone (140 parts), 1,4-bis(phenylethynyl)benzene (42 parts, Wako Pure Chemical Industries, Ltd.), and diphenyl ether (546 parts) were added to the reactor, and stirred at 250°C for 48 hours under a nitrogen atmosphere to react. 3,4-bis(4-methoxyphenyl)-2,5-diphenylcyclopenta-2,4-dienone was previously synthesized according to the description of Synthetic Metals vol.200, p85 to Zheng Bang Lim et al, (2015). After the reaction was terminated, it was returned to room temperature. The reaction solution was poured into methanol (1900 parts) under stirring to generate a precipitate, which was separated by filtration with a filter paper having a pore size of 1 μm. The precipitate was vacuum dried at 150° C. to obtain 155 parts of intermediate G0 (yield: 93%).

[Chemical formula xxxviii]

The obtained G0 was transferred to a new reactor, on which a stirrer, a nitrogen inlet pipe and a temperature control device were installed. The intermediate G0 (100 parts) and dichloromethane (941 parts) were added to the reactor, and the reaction temperature was maintained at -40°C under a nitrogen atmosphere. Thereafter, 372 parts of a dichloromethane solution (1 mol/L) of boron tribromide were slowly added dropwise. After the addition, the temperature of the reactor was slowly returned to room temperature (25°C), and the reaction was carried out while stirring at room temperature for 12 hours. Thereafter, water (1,000 parts) was slowly added to the stirring reaction solution to terminate the reaction. Thereafter, the dichloromethane in the reactant was removed by reduced pressure distillation at 80°C to obtain a precipitate. The precipitate was dissolved in a sufficient amount of stirring ethyl acetate (4,000 parts) and washed with ethyl acetate. Ethyl acetate was distilled off under reduced pressure, and the mixture was vacuum dried at 150° C. to obtain 92 parts of G1 (total yield: 90%, yield of G1 from G0: 97%).

[Chemical formula xxxix]

The NMR results of G1 were as follows, confirming that G1 had the above structure.

¹ H-NMR (400MHz in CDCl ₃ (1)/CF ₃ COOD (1)): 6.98-6.70 (m, 40H, Ph), 6.43 (m, 10H, Ph)

¹³ C-NMR (100MHz at CDCl ₃ (1)/CF ₃ COOD (1)): 157.4, 134.3, 133.6, 132.5, 130.5, 129.2, 127.9, 127.6, 127.2, 126.2, 116.4.

Synthesis Example 2 of G2

The synthesis was carried out in the same manner as in Synthesis Example 1 except that 1,4-bis(phenylethynyl)benzene was changed to 9,10-bis(phenylethynyl)anthracene. The total yield was 75%.

[Chemical formula xl]

The NMR results of G2 were as follows, confirming that G2 had the above structure.

¹ H-NMR (400MHz in CDCl ₃ (1)/CF ₃ COOD (1)): 7.91-7.39 (m, 46H, Ph), 6.43 (m, 8H, Ph)

¹³ C-NMR (100MHz at CDCl ₃ (1)/CF ₃ COOD (1)): 157.4, 134.3, 133.6, 133.1, 130.9, 130.5, 129.2, 127.9, 127.6, 126.2, 126.1, 125.6, 116.4

Synthesis Example 3 of G3

The synthesis was carried out in the same manner as in Synthesis Example 1 except that 1,4-bis(phenylethynyl)benzene was changed to 1,4-diethynylbenzene. The total yield was 85%.

[Chemical formula xli]

The NMR results of G3 were as follows, confirming that G3 had the above structure.

¹ H-NMR (400MHz in CDCl ₃ (1)/CF ₃ COOD (1)): 7.79-7.25 (m, 34H, Ph), 6.86 (m, 8H, Ph)

¹³ C-NMR (100MHz at CDCl ₃ (1)/CF ₃ COOD (1)): 157.4, 142.0, 140.9, 135.4, 133.8, 133.6, 130.5, 129.2, 127.9, 127.6, 127.2, 126.2, 126.1, 116.4.

Synthesis Example 4 of G4

Synthesis was performed in the same manner as in Synthesis Example 1 except that 3,4-bis(4-methoxyphenyl)-2,5-diphenylcyclopenta-2,4-dienone was replaced with 1,3-diphenyl-2H-cyclopenta[l]phenanthrene-2-one and 1,4-bis(phenylethynyl)benzene was replaced with 1,4-bis((4-methoxyphenyl)ethynyl)benzene. The total yield was 79%.

[Chemical formula xlii]

The NMR results of G4 were as follows, confirming that G4 had the above structure.

¹ H-NMR (400MHz in CDCl ₃ (1)/CF ₃ COOD (1)): 8.93 (m, 4H, Ph), 8.12-7.25 (m, 40H, Ph), 6.86 (m, 4H, Ph)

¹³ C-NMR (100MHz at CDCl ₃ (1)/CF ₃ COOD (1)): 157.4, 133.6, 132.5, 130.5, 129.6, 129.2, 128.3, 127.9, 127.6, 127.2, 126.6, 126.2, 126.1, 124.6, 123.9 ,122.6,122.5,122.1,120.8,118.7,116.4.

Synthesis Example 5 of G5

Synthesis was performed in the same manner as in Synthesis Example 1 except that 3,4-bis(4-methoxyphenyl)-2,5-diphenylcyclopenta-2,4-dienone was changed to 2,3,4,5-tetra(4-methoxyphenyl)cyclopenta-2,4-dienone and 1,4-bis(phenylethynyl)benzene was changed to 1,2-bis(4-methoxyphenyl)acetylene. The total yield was 80%.

[Chemical formula xliii]

The NMR results of G5 were as follows, confirming that G5 had the above structure.

¹ H-NMR (400MHz in CDCl ₃ ): 7.62 (m, 12H, Ph), 6.86 (m, 12H, Ph), 5.35 (m, 6H, OH).

¹³ C-NMR (100 MHz in CDCl ₃ ): 157.4, 134.3, 130.5, 126.2, 116.4.

Synthesis Example 6 of G6

Synthesis was carried out in the same manner as in Synthesis Example 1 except that 1,4-bis(phenylethynyl)benzene was changed to 4,4'-bis(phenylethynyl)-1,1'-biphenyl. The total yield was 75%.

[Chemical formula xliv]

The NMR results of G6 were as follows, confirming that it was the above structure.

¹ H-NMR (400MHz in CDCl ₃ (1)/CF ₃ COOD (1)): 7.62 (m, 8H, Ph), 7.52-7.51 (m, 24H, Ph), 7.41 (m, 6H, Ph), 7.25(m,8H,Ph), 6.86(m,8H,Ph).

¹³ C-NMR (100MHz at CDCl ₃ (1)/CF ₃ COOD (1)): 157.4, 139.7, 134.3, 133.6, 132.5, 130.5, 129.2, 127.9, 127.6, 127.2, 126.2, 116.4.

Synthesis Example 7 of G7

The synthesis was carried out in the same manner as in Synthesis Example 1 except that 1,4-bis(phenylethynyl)benzene was changed to 5'-phenyl-2',4',6'-tri(phenylethynyl)-1,1',3',1"-terphenyl. The total yield was 64%.

[Chemical formula xlv]

The NMR results of G7 were as follows, confirming that G7 had the above structure.

¹ H-NMR (400MHz in CDCl ₃ (1)/CF ₃ COOD (1)): 7.62 (m, 12H, Ph), 7.52-7.51 (m, 48H, Ph), 7.41 (m, 12H, Ph), 6.86(m,12H).

¹³ C-NMR (100MHz at CDCl ₃ (1)/CF ₃ COOD (1)): 157.4, 134.3, 133.6, 130.5, 129.2, 127.9, 127.6, 126.2, 116.4.

Synthesis Example 8 of G8

Synthesis was carried out in the same manner as in Synthesis Example 1 except that 3,4-bis(4-methoxyphenyl)-2,5-diphenylcyclopenta-2,4-dienone was replaced with 2,3,4,5-tetraphenylcyclopenta-2,4-dienone and 1,4-bis(phenylethynyl)benzene was replaced with 4,4'-(ethynyl-1,2-diyl)diphenylamine. The total yield was 58%.

[Chemical formula xlvi]

The NMR results of G8 were as follows, confirming that G8 had the above structure.

¹ H-NMR (400MHz in CDCl ₃ ): 7.54 (m, 4H, Ph), 7.52-7.51 (m, 16H, Ph), 7.41 (m, 4H, Ph), 6.58 (m, 4H, Ph), 6.27 ( br, 4H, NH ₂ ).

¹³ C-NMR (100 MHz in CDCl ₃ ): 144.5, 134.3, 133.6, 129.2, 128.7, 127.9, 127.6, 123.6, 119.8.

Comparative Example 1-1 Evaluation of Solubility of Comparative Example Compound 1

In order to evaluate the solubility of the following comparative example compound 1 described in Angew. Chem. Int. Ed. Engl. 36 (No. 15), p1607-(1997), the following test was performed.

Comparative Compound 1 as a solute was added to each solvent listed in Table 1 so as to be 10% by mass, and stirred and mixed at room temperature for 60 minutes. When the solute was not completely dissolved at 10% by mass, the addition amount was changed to 1% by mass, and mixing was performed in the same manner.

[Chemical formula xlvii]

The dissolution conditions of these solutes were visually confirmed and evaluated as follows.

A: Even when mixed at 10 mass %, the solute was completely dissolved.

B: When mixed at 10% by mass, the solute remained in an incompletely dissolved state, but when mixed at 1% by mass, the solute was completely dissolved.

C: Even when mixed at 1 mass %, the solute was not completely dissolved and remained.

Table 1

In the above table, the abbreviations are as follows: "7:3" means a liquid obtained by mixing at a volume ratio of 7:3. The same applies to the following.

PGME: Propylene glycol monomethyl ether

PGMEA: Propylene glycol 1-monomethyl ether 2-acetate

EL: Ethyl lactate

It was confirmed that the compound of the present application has high solubility in the solvent.

Examples 1-1 to 4, Reference Example 1-1 Evaluation of the solubility of the compounds of the present application and intermediate G0

The same test was performed as shown in Table 1, except that the solute was changed from Comparative Example Compound 1. The evaluation results are shown in Table 1.

Preparation Example 1 of Composition 1

The compounds in Table 1 were completely dissolved in a mixed solvent of PGME:PGMEA=7:3. The added amounts were as described in parts by mass in Table 2. This was filtered using a 0.2 μm fluororesin filter (SLFG025NS manufactured by Merck Millipore) to obtain Composition 1.

Preparation Examples 2 to 11 of Compositions 2 to 11, Comparative Preparation Examples 1 to 3 of Comparative Compositions 1 to 3

Compositions 2 to 11 and Comparative compositions 1 to 3 were obtained by performing the same operation except that the compound of Preparation Example 1 was changed to the compound, crosslinking agent, and thermal acid generator described in Table 1.

[Chemical formula xlviii]

交联剂1(旭有机材株式会社制造)

Crosslinking agent 1 (manufactured by Asahi Organic Materials Co., Ltd.)

[Chemical formula xlix]

热酸产生剂1。

Thermal acid generator 1.

As the thermal acid generator 1, a reagent obtained by mixing the above two compounds was used (in order from the left, the molar ratio is 20:21). All of them are manufactured by Tokyo Chemical Industry Co., Ltd.

[Chemical formula 1]

交联剂2(旭有机材株式会社制造)

Crosslinking agent 2 (manufactured by Asahi Organic Materials Co., Ltd.)

[Chemical formula]

交联剂3(本州化学工业株式会社制造)

Crosslinking agent 3 (manufactured by Honshu Chemical Industry Co., Ltd.)

[Chemical formula lii]

比较聚合物2

Comparison polymer 2

The polymer described in Patent Document 2. Mw=3,500, Mw/Mn=4.50

[Chemical formula liii]

比较化合物3

Comparative Compound 3

Evaluation of filling properties of Examples 2-1 to 11 and Comparative Examples 2-1 to 3

Compositions 1 to 11 and comparative compositions 1 to 3 were applied to an uneven SiN wafer in the following order, and the embedding characteristics were evaluated.

Using an MS-150A spin coater (manufactured by Mikasa Co. Ltd.), the composition was applied at 1,500 rpm to a SiN high-low difference wafer (manufactured by Advanced Materials Technology, Inc.), the SiN high-low difference wafer having a channel with a width and height of approximately 10 nm and 500 nm, respectively, and a top with a width of 10 nm. In an air atmosphere, it was baked on a hot plate at 250°C for 90 seconds and 450°C for 90 seconds in steps. It was further baked at 450°C for 1 hour in a nitrogen atmosphere to make a film from the composition. A slice of the wafer loaded with the film was made, and the channel portion was confirmed using a SEM (S-5500 manufactured by Hitachi High-Tech Fielding Corporation) photograph, and the filling property of the composition was evaluated as follows. The evaluation results are recorded in Table 2.

A: No grooves having voids or bubbles were confirmed, and the composition was well filled in the grooves.

B: The composition cannot be completely filled, and grooves with gaps or bubbles exist.

Evaluation of heat resistance of Examples 3-1 to 11 and Comparative Examples 3-1 to 3

Compositions 1 to 11 and comparative compositions 1 to 3 were applied to Si wafers in the following order, and heat resistance was evaluated.

Determination of film thickness reduction rate 1

The composition was applied to a Si bare wafer (manufactured by KST World Co. Ltd.) at 1,500 rpm using CLEAN TRACK ACT 12 (manufactured by Tokyo Electron Limited). The composition was baked on a hot plate at 250°C for 90 seconds and 450°C for 90 seconds in an air atmosphere to form a film. The film thickness of the film on the wafer was measured by an ellipsometer (M-2000D, manufactured by J.A. Woollam Japan Corporation) and was designated as "A".

Furthermore, the wafer was baked at 450° C. for 1 hour in a nitrogen atmosphere. The film thickness of the film on the wafer was measured by an ellipsometer and was designated as “B”.

The film thickness reduction rate 1 before and after baking at 450° C. for 1 hour was calculated by 100-B/A×100. The results are shown in Table 3.

Determination of film thickness reduction rate 2

The composition was applied to a Si bare wafer (manufactured by KST World Co. Ltd.) at 1,500 rpm using CLEAN TRACK ACT 12 (manufactured by Tokyo Electron Limited). The composition was baked on a hot plate at 250°C for 90 seconds in an air atmosphere to form a film. The film thickness of the film on the wafer was measured by an ellipsometer and was designated as "C".

Furthermore, the wafer was baked at 600° C. for 120 seconds in a nitrogen atmosphere. The film thickness of the film on the wafer was measured by an ellipsometer and was designated as “D”.

The film thickness reduction rate 2 before and after baking at 600° C. for 120 seconds was calculated by 100-D/C×100. The results are shown in Table 3.

Even when the film obtained from the compound of the present application is heated, the reduction in film thickness is small, confirming excellent heat resistance. In addition, even when a cross-linking agent and a thermal acid generator are added to the film obtained from the comparative polymer 2, the inhibitory effect on the reduction in film thickness under high temperature baking (600°C) is not very large, but in the case of the compound of the present application, a large inhibitory effect is confirmed.

Table 2

Table 3

Claims (8)

1. A method for manufacturing a semiconductor, comprising the steps of:

applying a layer of an underlayer film forming composition on a substrate,

curing the layer to produce an underlying film, wherein the layer is cured under such conditions that calcination is carried out at 150 to 650 ℃ for 30 to 180 seconds,

forming a layer of photoresist composition over the underlying film,

the photoresist composition is cured to form a photoresist layer,

exposing the substrate coated with the photoresist layer,

Developing the exposed substrate to form a resist pattern,

etching is performed with the resist pattern set as a mask,

the substrate is processed and the substrate is processed,

wherein the underlayer film forming composition comprises a semiconductor material composed of a compound represented by the following formula (8), (9), (10) or (11) and a solvent,

[ formula viii ]

[ chemical formula ix ]

[ chemical formula x ]

[ chemical formula xi ]

A is-OH or-NH ₂ ，

R ₁ Is hydrogen, -OH, -NH ₂ SH, or a direct bond to a phenyl ring,

R _1’ is hydrogen, -OH, -NH ₂ SH, or a direct bond to a phenyl ring,

R ₂ is hydrogen, -OH, -NH ₂ SH, or a direct bond to a phenyl ring,

R _2’ is hydrogen, -OH, -NH ₂ SH, or a direct bond to a phenyl ring,

R ₃ is hydrogen, -OH, -NH ₂ SH, or a direct bond to a phenyl ring,

R _3’ is hydrogen, -OH, -NH ₂ SH, or a direct bond to a phenyl ring,

n ₁ is 0, 1 or 2,

n ₂ is 0, 1 or 2,

n ₃ 0, 1 or 2, and

m is 0, 1, 2 or 3.

2. The method for producing a semiconductor according to claim 1, wherein the compound of formula (8), (9), (10) or (11) has 42 to 120 carbon atoms.

3. The method for manufacturing a semiconductor according to claim 1, wherein,

The aforementioned solvent is selected from: water, n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2, 4-trimethylpentane, n-octane, isooctane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, n-pentylnaphthalene, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, zhong Jichun, 2-ethylbutanol, zhong Gengchun, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonanol, 2, 6-dimethyl-4-heptanol, n-decanol, sec-undecanol trimethylnonanol, sec-tetradecanol, zhong Shiqi alkanol, phenol, cyclohexanol, methylcyclohexanol, 3, 5-trimethylcyclohexanol, benzyl alcohol, phenylmethyl methanol, diacetone alcohol, cresol, ethylene glycol, propylene glycol, 1, 3-butanediol, 2, 4-pentanediol, 2-methyl-2, 4-pentanediol, 2, 5-hexanediol, 2, 4-heptanediol, 2-ethyl-1, 3-hexanediol, diethylene glycol, dipropylene glycol triethylene glycol, tripropylene glycol, glycerol, acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, trimethylnonyl ketone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2, 4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, fenchyl, diethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1, 2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriethylene glycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, diethyl carbonate, methyl acetate, ethyl acetate, gamma-butyrolactone, gamma-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl amyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, ethylene glycol diacetate, methoxytriethylene glycol acetate, ethyl propionate, N-butyl propionate, isoamyl propionate, diethyl oxalate, di-N-butyl oxalate, methyl lactate, ethyl lactate, N-butyl lactate, N-pentyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, N-methylformamide, N-dimethylformamide, N-diethylformamide, acetamide, N-methylacetamide, N-dimethylacetamide, N-methylpropanamide, N-methylpyrrolidone, dimethylsulfide, diethylsulfide, thiophene, tetrahydrothiophene, dimethylsulfoxide, sulfolane, 1, 3-propane sultone, and mixtures of any of them.

4. The method for producing a semiconductor according to claim 1 or 3, wherein the amount of the semiconductor material of formula (1) is 2 to 40% by mass based on the entire underlayer film forming composition.

5. The method for manufacturing a semiconductor according to claim 1 or 3, further comprising a surfactant, a crosslinking agent, an acid generator, a radical generator, a substrate adhesion enhancer, or any mixture of any of them.

6. The method for manufacturing a semiconductor according to claim 1 or 3, further comprising a surfactant, a crosslinking agent, or an acid generator.

7. The method for manufacturing a semiconductor according to claim 1, further comprising the steps of:

wiring is formed in the processed substrate.

8. The method for manufacturing a semiconductor according to claim 1, wherein,

the substrate is an uneven substrate, and the difference between the height of the top and the bottom of the surface of the substrate is 10-10,000 nm.